ACID/BASE CATALIZED

REACTION
(a.k.a. Two-Stage Process)

Why a two stage process?

The single stage, base-catalyzed transesterification process we carried

out in previous labs is inefficient because soap is made.
Soap is formed when sodium ions from the lye or potassium ions from
the potassium hydroxide combine with free fatty acids (FFAs) present
in used vegetable oil, some virgin oils, and animal fats.
The soaps diminish the yield because they bond the methyl esters to
water.
The bonded esters get washed out at the washing stage but make
water separation more difficult (emulsification occurs) and increase
water consumption.
An acid-catalyzed esterification process before the base-catalyzed
transesterification process will eliminate most of the free fatty acids
from the vegetable oil.
FFAs = bad.

Process Overview: Stage 2

The second-stage process is transesterification and uses basic catalyst

as usual, but uses less than the single stage process
The sulfate ion in the sulfuric acid combines with the sodium or
potassium ion during the second-stage reaction to form a water-soluble
salt (sodium or potassium sulfate) that gets removed during the water
wash phase.
No sulfur remains in the biodiesel fuel product.

Process Overview: Stage 1

The first-stage process is not trans-esterification it is simple

esterification
We turn FFAs into biodiesel thus significantly decreasing the possibility
of saponification (soap making)
We use an acid as the catalyst for the esterification of the FFAs
Sulfuric acid is battery acid and needs to be 95% pure (battery acid is
around 50%)
Sulfuric acid is one of the most common chemicals on Earth, just like
lye. It is also extremely corrosive so wear chemical protective gloves
and eye protection when handling strong acids.

Pretreatment of High Free

Fatty Acid Feedstocks
Biodiesel feedstocks vary in the amount of
free fatty acids they contain:
Refined vegetable oils
< 0.05%
Crude soybean oil
0.3-0.7%
Restaurant waste grease
2-7%
Animal fat
5-30%
Trap grease
75-100%

Alkali Catalysts
Not suitable for high FFA feeds because of soap
formation.
Typical catalyst amounts:
Sodium hydroxide:
1% of triglyceride weight
Potassium hydroxide:
1% of triglyceride weight
Sodium methoxide:
0.25% of triglyceride
weight

High FFA feeds must be

pretreated
Four methods
1. Enzymatic methods very costly, not
currently a popular choice.
2. Glycerolysis
3. Acid catalysis
4. Acid catalysis followed by base catalysis.

Glycerolysis
Add glycerol to high FFA feedstock with
catalyst (ZnCl) at 200C.
Converts FFAs to monoglycerides and
diglycerides. These can be transesterified to
methyl esters with a base catalyst.
Water formed by
FFA + glycerol >> monoglyceride + water
is vented as it is formed.

Glycerolysis

Disadvantages:
Requires high temperature, 200C
Fairly slow process.
Requirement for clean glycerol is not
known.

Approach for low levels of FFA

Can add additional catalyst and allow soap
formation (similar to caustic stripping).
It takes one mole of catalyst to neutralize one mole
of FFA.
Sodium hydroxide:
[%FFA](0.144) + 1 %
Potassium hydroxide:
[%FFA](0.197)/0.86 + 1 %
Sodium methoxide:
[%FFA](0.190) + 0.25 %
This approach will work up to 5-6% FFA, less if
emulsifiers or water are present.

Acid Catalysis
Use acid such as sulfuric acid to catalyze
both esterification and transesterification
reactions.
Esterification of FFA is fast (1 hour) but
transesterification is slow (2 days) at 60C.
Water formation by
FFA + methanol >> methyl ester + water
Can be a problem.

Acid catalysis followed by base

catalysis
Use acid catalysis for conversion of FFAs to
methyl esters, until FFA < 0.5%.
Then, add additional methanol and base
catalyst to finish the reaction.

Lab Procedure

Measure the acid value of the WVO sample

Note: Acid value is twice the %FFA
Measure out 200g of WVO sample
Heat sample to 60oC
Measure out 2.25g methanol for every gram of
FFA in the WVO sample
Calculate amount of sulfuric acid to add
0.05 g of sulfuric acid for every gram of FFA in
sample

Lab Procedure (part 2 )

Add the acid to the alcohol

Gently agitate the alcohol-acid mixture until
completely mixed
Add the alcohol-acid mixture to the 200g of
WVO sample
Agitate mixture at 60oC for 1 hour
Let mixture settle- Methanol-water mixture will rise to

After the mixture cools, drain a sample from the

the top

bottom fraction and measure new FFA level via acid

value measurement

(Directions taken from Iowa State Lab procedure,Pretreatment of High Free Fatty Acid
Feedstocks)

Acid catalysis followed by base

catalysis
After measuring the acid value or %FFA, your results will
Determine your next step:
If FFA is > 0.5%, return to step 2 with new FFA level. If
FFA is < 0.5%, proceed to step 7.
Add an amount of methanol equal to 0.217 x [grams of
unreacted triglycerides] and
an amount of sodium methoxide equal to
[0.25 + (%FFA)0.190]/100 x [grams of unreacted
triglycerides].
Mix the sodium methoxide with the methanol and then add to
the oil.
Agitate for 1 hour at 60C.

References
Canakci, M. and J. Van Gerpen, 1999, Biodiesel
Production via Acid Catalysis, ASAE
Transactions, 42(5):1203-1210.
Canakci, M. and J. Van Gerpen, 2001, Biodiesel
Production from Oils and Fats with High Free
Fatty Acids, ASAE Transactions, 44(6):14291436.
www.me.iastate.edu/biodiesel